Janthon Patanachai, Kozlov Sergey M, Viñes Francesc, Limtrakul Jumras, Illas Francesc
Departament de Química Física and Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, c/Martí i Franquès 1, 08028, Barcelona, Spain.
Department of Chemistry and Center of Nanotechnology, Kasetsart University, Bangkok 10900, Thailand.
J Chem Theory Comput. 2013 Mar 12;9(3):1631-40. doi: 10.1021/ct3010326. Epub 2013 Mar 1.
The performance of various commonly used density functionals is established by comparing calculated values of atomic structure data, cohesive energies, and bulk moduli of all transition metals to available experimental data. The functionals explored are the Ceperley-Alder (CA), Vosko-Wilk-Nussair (VWN) implementation of the Local Density Approximation (LDA); the Perdew-Wang (PW91) and Perdew-Burke-Ernzerhof (PBE) forms of the Generalized Gradient Approximation (GGA), and the RPBE and PBEsol modifications of PBE, aimed at better describing adsorption energies and bulk solid lattice properties, respectively. The present systematic study shows that PW91 and PBE consistently provide the smallest differences between the calculated and experimental values. Additional calculations of the (111) surface energy of several face centered cubic (fcc) transition metals reveal that LDA produces the most accurate results, while all other functionals significantly underestimate the experimental values. RPBE severely underestimates surface energy, which may be the origin for the reduced surface chemical activity and the better performance of RPBE describing adsorption energies.
通过将所有过渡金属的原子结构数据、内聚能和体模量的计算值与现有实验数据进行比较,确定了各种常用密度泛函的性能。所研究的泛函包括局域密度近似(LDA)的Ceperley-Alder(CA)、Vosko-Wilk-Nussair(VWN)实现;广义梯度近似(GGA)的Perdew-Wang(PW91)和Perdew-Burke-Ernzerhof(PBE)形式,以及分别旨在更好地描述吸附能和体固体晶格性质的PBE的RPBE和PBEsol修正。目前的系统研究表明,PW91和PBE始终在计算值和实验值之间提供最小的差异。对几种面心立方(fcc)过渡金属的(111)表面能的额外计算表明,LDA产生了最准确的结果,而所有其他泛函都显著低估了实验值。RPBE严重低估了表面能,这可能是表面化学活性降低的原因,也是RPBE在描述吸附能方面表现更好的原因。